Water-insoluble azo dyestuffs



Patented Dec. 24, 1935 PATENT OFFICE WATER-INSOLUBLE AZO DYESTUFFS Ernst Fischer, Frankfort-en-the-Main-Hochst, Germany, assignor to General Aniline Works, Inc., New York, N. Y., a corporation of Delaware N Drawing. Application September 20, 1933, Serial No. 690,291. In GermanySeptember 24,

4' Claims.

The present invention relates towater-insoluble azo-dyestuffs; more particularly it relates to compounds of the following general formula:

wherein X means an alkyl or alkoxy group, R stands for hydrogen, an alkyl, aryl, aralkyl or hydroaromatic radical and R1 stands for a radical of the benzene or naphthalene series.

I have found that valuable red pigment dyestuffs are obtainable by coupling the diazo compounds of bases of the general formula:

whereinX' means an alkyl or alkoxy group and R stands for hydrogen, an alkyl, aryl, aralkyl or hydroaromatic radical, with arylides of 2,3-nydroxynaphthoic acid, only such components being'used as do not contain groups lending solubility, such as the sulfonic acid or carboxylic acid group.

The dyestuffs may be used for the preparation of lakes which are fast to oils and very fast to light as Welles for coloring masses which are capable of being formed, especially naturalrubber or synthetic products having properties similar to those of natural rubber. By incorporating the dyestuffs with rubber products mixtures are obtained which are fast to vulcanization and very fast to light. These good properties are surprising because the diazo compounds of the bases which are comprised by the above formula are unsuitable for the preparation of dyeings on the fiber since a great part of the dyestuffs is removed from the fiber even by soaping at the boil.

The following examples serve to illustrate the sponds to the following formula:

SOz-NH1 N II i o awn-O is filtered-by suction, washed well and dried. It forms a red powder. Lakes which have been prepared in known manner from this dyestufi' are fast to oils and yield red tints which are fast to light.

The coupling may also beeffected in the presence of a substratum adapted for the production of lakes.

(2) parts of 3-amino-4-methylbenzene-1'- sulfonic acid-methylamide are diazotized as usual. The diazo solution is rendered neutral to Congo paper by means of sodium acetate and is introduced, while stirring, into a solution of 14.65 parts of 2',3-hydroxynaphthoy1 1 amino-4- methoxybenzene in dilute caustic soda solution. The red dyestuff, thus formed, which corresponds to the following formula nao is filtered by suction, washed well and dried. It may be used in known manner for the preparation of lakes which are fast to oils and yield red tints of good fastness to light.

(3) By using in Example 2, instead of 2,3-hydroxynaphthoyll amino 4 methoxybenzene, 2,3-hydroxynaphthoyl-l-amino-Z-methoxybenzene, there are likewise obtained red lakes which have similarly good fastness properties and shades of a somewhat more yellowish hue than those of the lakes prepared according to Example 2.

(4) A pigment dye is prepared from 13.8 parts of 3-amino-4-methylbenzene-l-sulfonic benzylamide and 14.65 parts of 2,3'-hydroxynaphthoyl-1-amino-2-methoxybenzene in the manner described in Examples 1 and 2, it yields red lakes which are fast to oils and to light.

(5) The pigment dyestuff which is prepared according to the statements in Example 1 from 14.2 parts of 3-amino-4methoxybenzene-l-sulionic acid-cyclohexylamide and 14.65 parts of 2,3-hydroxynaphthoyl-l-amino-Z-methoxybenzene forms a red powder from which red lakes of good fastness to oils and to light may be prepared in known manner.

(6) From 13.1 parts of 3-amino-4-methylbenzene-l-sulfanilide and 14.65 parts of 2,3 hy- 'droxynaphthoyl 1 amino 2 methoxybenzenethere is obtained in the manner described in Examples 1 and 2 a red pigment dye which yields according to known methods red lakes which are fast to oils and to light.

(7) A pigment dye which is adapted for color- .26 parts of sulfur, 5 parts of zinc white, 1- part of mercapto-benzothiazol, 0.2 part of hexamethylenetetramine, 60 parts of calcium carbonate, 0.6 part of ozocerite, 10 parts 01 lithopone, 5 parts of titanium dioxide and 4 parts of the aforesaid dyestufi. The mixture is vulcanized in a vulcanization press for 12 minutes at a steam pres- 7 sure of 3 atmospheres above atmospheric'pressure. There is obtained a very pure, vivid red vulcanizate which is very fast to light, neither .bleeds nor gives rise to that phenomenon which is known as blushing or efiiorescence when the rubber articles are stored.

A mixture of crepe rubber, the usual admixtures and 4 parts of the aforesaid dyestuff is vul- 'canized in the cold by immersing it in a. solution of sulfur chloride in benzine. The vulcanizate, thus obtained, has properties which are the same as those of the vulcanizate described above.

(8) By using in Example 7, instead of 10.1

' parts of 3-amino-4methoxybenzene-l-sulfamide,

10.8 parts of 3-amino-4-methoxybenzene-l-sulacidthe product obtained according to Examples '7 and 8.

(10) A red pigment dye is obtained in the manner described in- Examples 1 and 2 from 11.5'

parts acid-methylamide and 14.65 parts of 2 ,3-hydroxynaphthoyl- 1 amino 4 methoxybenzene. The lake prepared therefrom by known methods is fast to oils and yields red tints which are fast to light.

The following dyestuffs, among others, are capable of production in accordance with this invention:

Diazo compound oi' Combined withh 3 amino 4 methyl S ads benzene -1- sulfonic 2, 3-hydroxynaphtl10ylacid- 1 l-amino-napthaleno Red. 2 2-amino-napl1tl1alene Red. 3 l-amino-3-metl1yl-benzene Red. 4 l-amino- 2 -methoxy- 5-chloroed benzene. 5 1-amino- 2 -metl1oxy- 4'ch1oro- Red.

benzene. 6 Amide 1-amino-2-ethoxy-benzene Red. 7 Methylamide l-amino-4-chloro-benzene Red. 8 Methylamide l-amino-2-methoxy-5-chloro- Red.

benzene. 9 Methylamide l-amino-2-methoxy-4-chloro- Red.

benzene. 10 1-amino-2-methoxy-benzene Red. 11 l-amino-4methoxy-benzene. Red. 12 1-amino-2-methoxy-benzene Red. 13 l-aminoi-methoxy-benzene Red. 14 n-butylamide l-amino-2-methoxy-benzene. Red. 15 n-butylamide l-aminoi-methoxy-benzene Red. 16 n-butylamide. l-amino- 2,4 -d1methoxy- 5 Red.

. chlorobenzene. 17 Anillde '1-amino-4-methoxy-benzene Red. 18 Anilide l-amino- 2-1nethoxy-4-chloro- Red.

' benzene. 19 Ortho-chloro-anilide 1-amino-2-methoxy-benzene; Red. 20 Ortho-chlor0-anilide i-aminoi-methoxy-benzene Red. 21 Benzylamide 1-amino-4-methoxy-benzene Red. 22 Cyclohexylamlde. Amino-benzene Red 23 Oyclohexylamidef 1-amino-2-methcxy-benzene Red. 24 Oyclohexylamide l-aminoi-methoxy-benzene Red.

3-amino- 4 -methoxybenzene- 1 -sulfonic acid- 25 Methylamide l-amino-2-meth0xy-benzene Red. 26 Methylamide l-amino-i-methoxy-benzene Red. 27 Ethylann'de; Aminobenzene Red, 28 Benzylamide 1-amino-2-methoxy-benzene Red. 29 Benzylamidm 1-amino-4-methoxy-benzene Red. 30 Oyclohexylamid Aminobenzene Red. 31 Oyclohexy1amide 1-amino-4-metl10xybenzene Red.

Since an object of the present invention is to produce dyestuffs of good fastness properties which dyestuffs are insoluble in water, it is to be understood that the aromatic nuclei of the general formulae appearing in the appended claims do not contain any substituents which are known to render the dyestuffs soluble in water. Substituents of this kind are, for instance, the sulfonic acid and carboxylic acid group.

I claim:

1. The water-insoluble azo-dyestufis of the following general formula:

of 3-amino-4-ethoxybenzene-l-sulfonic yielding, when mixed with rubber products, vivid red dyeings of a very good fastness to light and to vulcanization.

3. The water-insoluble azo-dyestuff of the following formula:

yielding, when mixed with rubber products, red dyeings with a yellow hue of a very good fastness to light and to vulcanization.

4. The water-insoluble azo-dyestufl's of the following formula:

II N yielding red lakes of very good fastness to light and to oils.

ERNST FISCHER. 

